Complex sulfur

The dinuclear ion Mo2(S2) g (F - prepared from the reaction of molybdate and polysulfide solution (13) is a usehil starting material for the preparation of dinuclear sulfur complexes. These disulfide ligands are reactive toward replacement or reduction to give complexes containing the Mo2S " 4 core (Fig. 3f). 

More recendy, molecular molybdenum-sulfur complexes and clusters have been used as soluble precursors for M0S2 in the formulation of lubricating oils for a variety of appHcations (70). Presumably, the oil-soluble molybdenum—sulfur-containing precursors decompose under shear, pressure, or temperature stress at the wear surface to give beneficial coatings. In several cases it has been shown that the soluble precursors are trifunctional in that they not only display antifriction properties, but have antiwear and antioxidant characteristics as weU. In most cases, the ligands for the Mo are of the 1,1-dithiolate type, including dithiocarbamates, dithiophosphates, and xanthates (55,71). 

R SiH and CH2= CHR interact with both PtL and PtL 1. Complexing or chelating ligands such as phosphines and sulfur complexes are exceUent inhibitors, but often form such stable complexes that they act as poisons and prevent cute even at elevated temperatures. Unsaturated organic compounds are preferred, such as acetylenic alcohols, acetylene dicarboxylates, maleates, fumarates, eneynes, and azo compounds (178—189). An alternative concept has been the encapsulation of the platinum catalysts with either cyclodextrin or in thermoplastics or siUcones (190—192). 

Sulfur Complexes. Silver compounds other than sulfide dissolve in excess thiosulfate. Stable silver complexes are also formed with thiourea. Except for the cyanide complexes, these sulfur complexes of silver are the most stable. In photography, solutions of sodium or ammonium thiosulfate fixers are used to solubilize silver hahdes present in processed photographic emulsions. When insoluble silver thiosulfate is dissolved in excess thiosulfate, various silver complexes form. At low thiosulfate concentrations, the principal silver species is Ag2(S203) 2j high thiosulfate concentrations, species such as Ag2(S203) 3 are present. Silver sulfide dissolves in alkaline sulfide solutions to form complex ions such as Ag(S 2 Ag(HS) 4. These ions are... 

Molybdenum hexafluoride. 3,1412 Molybdenum-iron-sulfur complexes, 4,241 Molybdenum oxide amino acid formation prebiotic systems, 6, 872 Molybdenum storage protein microorganisms, 6, 681 Molybdenum telluride, 3, 1431 Molybdenum tetraalkoxides physical properties, 2, 347 Molybdenum tribromide, 3,1330 Molybdenum trichloride, 3,1330 Molybdenum trifluoride, 3, 1330 Molybdenum trihalides, 3, 1330 bond lengths, 3, 1330 magnetic moments, 3,1330 preparation, 3,1330 properties, 3, 1330 structure, 3,1330 Molybdenum triiodide, 3,1330 Molybdenum trioxide complexes, 3, 1379 Molybdenum triselenide, 3, 143)... 

The first step consists in the attack of a proton on the W-H bond to yield a labile dihydrogen intermediate (Eq. (3)) that rapidly releases H2 to form a coordi-natively unsaturated complex (Eq. (4)). This complex adds water in the next step to form an aqua complex (Eq. (5)) that completes the reaction by substituting the coordinated water by the X anion (Eq. (6)). Steps (3)-(6) are repeated for each W-H bond and the factor of 3 in the rate constants appears as a consequence of the statistical kinetics at the three metal centers. The rate constants for both the initial attack by the acid (ki) and water attack to the coordinatively unsaturated intermediate (k2) are faster in the sulfur complex, whereas the substitution of coordinated water (k3) is faster for the selenium compound. 

Nodule-forming bacteria (legume bacteria) live in symbiosis with the root system of legumes (e.g. beans). They can reduce nitrogen to ammonia with the aid of a molybdenum-sulfur complex. 

As the dinuclear metal-sulfur complexes that can exhibit excellent ability to serve as the precursors to the tailored metal-sulfur clusters, those with the M2S4 cores are known to be used for synthesizing cubane-type and relating sulfido clusters. These include the reactions that start from the complexes having Mo( t-SH)2(jt-S)2Mo,38 M(p-S2)(p-S)2M (M = V,39 Mo40), Ru(p-S2)2Ru,41 and MS(p-S)2MS (M = Mo, W,42 Re,43 Ti44) cores, which are summarized in Figure 10. 

Unfortunately, there has been little computational work on these interesting complexes hence, we will mostly consider complexes formed with shallow-level defects in the next section. There has, however, been a treatment of hydrogen-sulfur complexes in silicon by Yapsir et al. (1988) and a recent treatment of hydrogen-oxygen complexes by Gutsev et al. (1989), which we now describe. 

Figure 6.3 Energy changes for N2 reduction in the absence (top) or presence (bottom) of metal-sulfur complexes. (Adapted with permission from Figure 7b of Sellman, D., Sutter, J. Acc. Chem. Res., 1997, 30, 460-469. Copyright 1997, American Chemical Society.)...

To successfully describe the structure and function of nitrogenase, it is important to understand the behavior of the metal-sulfur clusters that are a vital part of this complex enzyme. Metal-sulfur clusters are many, varied, and usually involved in redox processes carried out by the protein in which they constitute prosthetic centers. They may be characterized by the number of iron ions in the prosthetic center that is, rubredoxin (Rd) contains one Fe ion, ferredoxins (Fd) contain two or four Fe ions, and aconitase contains three Fe ions.7 In reference 18, Lippard and Berg present a more detailed description of iron-sulfur clusters only the [Fe4S4] cluster typical of that found in nitrogenase s Fe-protein is discussed in some detail here. The P-cluster and M center of MoFe-protein, which are more complex metal-sulfur complexes, are discussed in Sections 6.5.2. and 6.5.3. 

Gold-sulfur complexes, 72 700 Gold tribromide, physical properties of,... 

Molybdenum metalworking, 17 10-11 Molybdenum mill products, 17 9-10 Molybdenum-nickel alloys, 17 102 Molybdenum ore, U.S. exports of, 17 3t Molybdenum oxidation states, 17 20 Molybdenum oxides, 17 38 Molybdenum pentachloride, 17 23 Molybdenum-rhenium alloys, 17 15 Molybdenum sulfide, poisons in representative reactions, 5 258t Molybdenum-sulfur complexes, molecular, 17 37... 

Fig. 46. Schematic structure of the iron-sulfur complex in two-iron ferredoxin and adrenodoxin. (Adapted from Ref. 267)...

The presence of high-molecular weight p-sulfur with chain structure seemed improbable since the sulfur was not extractable with boiling toluene. The p-sulfur is known to convert to the soluble ring structure (Sg) rather rapidly at 115°. Wibaut (119) thought the formation of a carbon-sulfur complex similar to the surface oxide formed with oxygen very likely. He was not able, however, to analyze definite surface groups. Hofmann and Nobbe (123) established that the sulfur content was dependent on the specific surface area. Enoksson and Wetterholm (124) confirmed by X-ray diffraction that no crystalline sulfur was present in exhaustively extracted charcoal with 13% sulfur content. 

Carrell, H. L., dusker, J. P., Job, R., and Bruice, T. C. (1977). A synthetic tetranuclear iron-sulfur complex with ionized side chains The crystal structure of (Fe4S4(S(CH2)aCOO)4) -(Na5-N(C4H9)4) -5C6H9NO./. Am. Chem. Soc. 99, 3683-3690. 

The recent discovery that a class of electron mediating proteins, the ferredoxins (Sec. IVE2), characteristically contain two or more iron atoms bridged by sulfur atoms has stimulated interest in polynuclear iron-sulfur complexes. It seems appropriate therefore to review here what little is known about such species. 

A large part of the research involving metal-sulfur complexes (metal = molybdenum or iron) is aimed at designing functional models of the active site of nitrogenase, the iron-molybdenum cofactor, EeMo—CO [4-8, 12, 13]. Only a very... 

Table 6.1 Solid-state luminescence of dinuclear gold-sulfur complexes.

The already voluminous review literature on clusters will be considered as a basis for this review. The topics treated so far are clusters in general (109, 241) and in connection with metal-metal bonding (30, 338, 380), special types of clusters like those with TT-acceptor ligands (231), hydrides (233), carbonyls (85, 86) or methinyl tricobalt enneacarbonyls (313, 317) properties of clusters like structures (56, 316), fluxionality (110), mass spectra (226), vibrational spectra (365), and redox behavior (292). Clusters have been treated in the context of metal carbonyls (3, 4), metal sulfur complexes (2, 381), and in relation to coordination polyhedra (297). Reviews... 

The structure of sodalite, Na lsSiaO Gl, a representative crystal of the framework class, is shown in Figure 13-13. It is interesting that the same framework is present in ultramarine (lapis lazuli).07 In the ultramarines sulfur complexes, Sx—, to which the blue color is attributed, are present in place of chlorine. The selenium and tellurium analogues are blood-red and yellow, respectively. 

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